Patent GB-653822-A (GB)
Title: Stabilization of polymeric organic compounds
IPC: C08K13/02
Filed: 1948-02-07
Abstract: Polymers and copolymers of a halogen-containing compound are stabilized by the incorporation of (a) 0.01 to 0.1 per cent by weight of an inorganic peroxide, and (b) 0.001 to 0.05 per cent by weight of a metal salt of an acid stronger than metaboric whose 1 per cent aqueous solution or dispersion has a pH of 8 to 12, in amounts sufficient to render the composition alkaline.  Polymers specified are polyvinyl chloride and fluoride, polyvinylidene chloride, polychloroprene, and copolymers of vinyl chloride with vinyl acetate or vinylidene chloride.  The polymers may be in the form of an aqueous emulsion, a dispersion in an inert organic liquid, or a solution.  The peroxide may be hydrogen peroxide, peroxides, hydroperoxides or ozonides of Li, Na, K, Mg, Ca, Sr, Ba, Cr, Mn, Fe, Cu, Zn, Cd, Al, Sn, Pb, Sb, Ti, and Ag to which traces of a metallic silicate, e.g. magnesium silicate, may be added; complexes of hydrogen peroxide and salts of the above-listed metals, e.g. Na, Mg, Ba, or Cd perborates, per mono-di- or tri- or pyro-phosphoric acid salts or percarbonic acid salts.  The metal salts (b) may be normal or acid and derived from oxyacids of Sb, As, C, Cr, P, Si, Pb or Sn, such as ortho, pyro, tri, tetra, meta, or perdi-phosphoric acids; or from carbonic, formic, acetic, proprionic, oxalic, succinic, maleic, fumaric, diglycollic, dilactic, tartaric, citric, benzoic, or phthalic acids; in particular, calcium hydrogen or tri-calcium phosphate or a mixed salt, calcium di-sodium pyrophosphate or a mixture of di-sodium hydrogen phosphate with tri-calcium or sodium phosphate may be used.  Organo-metallic salts containing methyl, ethyl, or propyl alcohol, ethylene, propylene or diethylene glycol or glycerine, e.g. sodium or calcium glycero-phosphate, sodium amyl thiophosphonate, sodium salts of phosphated castor oils, sodium capryl, amyl or ethyl phosphate, or sodium potassium ethyl phosphate may also be used.  Plasticizers such as esters of phthalic, sebacic, glycollic, oleic, ricinoleic, toluene, sulphonic, or stearic acid, in particular di-ethyl hexyl phthalate, dibutyl sebacate, glycol sebacate polyester, tricresyl phosphate, butyl "Cellosolve" (Registered Trade Mark), stearate, coconut oil, blown castor oil; lubricants, e.g. stearic acid, diethyleneglycol mono-stearate; fillers or pigments and opacifiers may be added.  Numerous examples show the use of compounds specified above and in addition, di-potassium hydrogen phosphate, lead phosphate, magnesium ammonium phosphate, lead meta-, ortho-, and pyro-phosphate, barium meta-phosphate, cadmium carbonate, basic lead carbonate, commercial lead silicate, sodium bi-, per- and normal carbonates, and a sodium pyrophosphate - hydrogen peroxide complex.  The ingredients are ground and incorporated by milling at normal or elevated temperatures and the products may be calendered to form films.  The Specification as open to inspection under Sect. 91 describes also the use of organic peroxides, e.g. benzoyl, succinyl, acetyl, toluyl, p-bromobenzoyl, anisoyl, chloracetyl peroxides and peracetic and perbenzoic acids; hydroperoxides, e.g. tetralin, 1-hydroxy-cyclopentyl, hexyl, heptyl or octyl hydroperoxide-1, and tertiary butyl hydroperoxide, and a petroleum hydrocarbon hydroperoxide mixture and other polymers such as polymerized vinyl acetate, styrene, methyl and ethyl methacrylates, methyl acrylate, acrylonitrile, ethylene, isobutylene, isoprene, butadiene, vinyl alcohol, butyral or formal, butadiene-styrene, acrylonitrile-butadiene.  In examples of the use of the copolymers, zinc oxide, mercaptobenzothiazole, tetraethyl thiuram disulphide, sulphur, clay, and benzothiazyldisulphide are added. This subject-matter does not appear in the Specification as accepted.ALSO:Polymers and copolymers of a halogen containing compound are stabilized by the incorporation of (a) 0.01 to 0.1 per cent by weight of an inorganic peroxide, and (b) 0.001 to 0.05 per cent by weight of a metal salt of an acid stronger than metaboric whose 1 per cent aqueous solution or dispersion has a pH of 8 to 12, in amounts sufficient to render the composition alkaline.  Polymers specified include polychloroprene.  The polymers may be in the form of an aqueous emulsion, a dispersion in an inert organic liquid, or a solution.  The peroxide may be hydrogen peroxide, peroxides, hydroperoxides or ozonides of Li, Na, K, Mg, Ca, Sr, Ba, Cr, Mn, Fe, Cu, Zn, Cd, Al, Sn, Pb, Sb, Ti, and Ag, to which traces of a metallic silicate, e.g. magnesium silicate, may be added; complexes of hydrogen peroxide and salts of the above listed metals, e.g. Na, Mg, Ba, or Cd perborates, per mono-di- or tri- or pyrophosphoric acid salts or percarbonic acid salts.  The metal salts (b) may be normal or acid and derived from oxyacids of Sb, As, C, Cr, P, Si, Pb or Sn, such as ortho-, pyro-, tri-, tetra-, meta- or perdi-phosphoric acids; or from carbonic, formic, acetic, proprionic, oxalic, succinic, maleic, fumaric, diglycollic, dilactic, tartaric, citric, benzoic, or phthalic acids; in particular, calcium hydrogen or tri-calcium phosphate or a mixed salt, calcium, di-sodium pyrophosphate or a mixture of di-sodium hydrogen phosphate with tri-calcium or sodium phosphate may be used.  Organo-metallic salts containing methyl, ethyl or propyl alcohol, ethylene, propylene or diethylene glycol or glycerine, e.g. sodium or calcium glycerophosphate, sodium amyl thiophosphonate, sodium salts of phosphated castor oils, sodium capryl, amyl or ethyl phosphate, or sodium potassium ethyl phosphate may also be used.  Plasticizers such as esters of phthalic, sebacic, glycollic, oleic, ricinoleic, toluene sulphonic, or stearic acid, in particular di-ethyl hexyl phthalate, dibutyl sebacate, glycol sebacate polyester, tricresyl phosphate, butyl "Cellosolve" (Registered Trade Mark), stearate, coconut oil, blown castor oil; lubricants, e.g. stearic acid, diethyleneglycol mono-stearate; fillers or pigments and opacifiers may be added.  Numerous examples show the use of compounds specified above and in addition, di-potassium hydrogen phosphate, lead phosphate, magnesium ammonium phosphate, lead meta-, ortho-, and pyro-phosphate, barium meta-phosphate, cadmium carbonate, basic lead carbonate, commercial lead silicate, sodium bi-, per- and normal carbonates, and a sodium pyrophosphate-hydrogen peroxide complex.  The ingredients are ground and incorporated by milling at normal or elevated temperatures and the products may be calendered to form films.  The Specification as open to inspection under Sect. 91 describes also the use of organic peroxides, e.g. benzoyl, succinyl, acetyl, toluyl, p-brombenzoyl, anisoyl, chloracetyl peroxides and peracetic and perbenzoic acids, hydroperoxides, e.g. tetralin, 1-hydroxy-cyclopentyl, hexyl, heptyl or octyl hydroperoxide-1, and tertiary butyl hydroperoxide, and a petroleum hydrocarbon hydroperoxide mixture and other polymers such as chlorinated paraffin waxes, rubbers or diphenyls, polymerized vinyl acetate, styrene, methyl and ethyl methacrylates, methyl acrylate, acrylonitrile, ethylene, isobutylene, isoprene, butadiene, vinyl alcohol, butadiene-styrene, acrylonitrile-butadiene.  In examples of the use of the two copolymers, zinc oxide, mercaptobenzothiazole; tetraethyl thiuram disulphide, sulphur, clay, and benzothiazyldisulphide are added.  This subject-matter does not appear in the Specification as accepted.